Treatment of silver halide photographic material

ABSTRACT

in which R&#39;&#39; represents -CH2COOM or -CH2CH2OH and M has the same meaning as described.   In a method for the development of an exposed silver halide photographic material including a prehardening treatment with an aldehyde hardener prior to developing, the improvement which comprises treating said silver halide photographic material between said prehardening and said developing with a bath containing a compound represented by the following general formula (I) R-NH2 I. in which R represents -SO3M, -SO2NH2, -CH2COOM or -C(CH2OH)3 and M represents an atom or group capable of imparting water solubility, or the following general formula (II)

United States Patent [191 Shimamura et al.

[ Nov. 26, 1974 TREATMENT OF SILVER HALIDE PHOTOGRAPHIC MATERIAL [73]Assignee: Fuji Photo Film Co., Ltd.,

Kanagawa, Japan [22] Filed: Sept. 24, 1973 [2l] Appl. No.: 399,897

[30] Foreign Application Priority Data Sept. 26, 1972 Japan 47-96466[52] US. Cl. 96/50 R, 96/50 PT, 96/66 R [51] Int. Cl G03c 5/26 [58]Field of Search..... G03c/5/30; 96/50 PT, 50 R, 96/66, 66.5

[56] References Cited UNITED STATES PATENTS 3 l68,40() 2/1965 Blackmeret al 96/66 3,647,449 3/1972 Malloy 96/50 3,649,281 3/l972 lwano et al.96/50 PT Primary Examiner-Mary F. Kelley Attorney, Agent, orFirm-Sughrue, Rothwell, Mion, Zinn & Macpeak [57] ABSTRACT In a methodfor the development of an exposed silver halide photographic materialincluding a prehardening treatment with an aldehyde hardener prior todeveloping, the improvement which comprises treating said silver halidephotographic material between said prehardening and said developing witha bath containing a compound represented by the following generalformula (l) R-NH l. in which R represents SO M, S() NH CH COOM or C(CHOl-l) and M represents an atom or group capable of imparting watersolubility, or the following general formula (II) NH (II) 7 Claims, NoDrawings TREATIVENT OF SILVER I-IALIDE PHOTOGRAPHIC MATERIAL BACKGROUNDOF THE INVENTION 1. Field of the Invention V This invention relates to amethod for developing a silver halide photographic material and, moreparticularly, it is concerned with a method of removing the fog formedin the hardening treatment of a silver halide emulsion layer.

2. Description of the Prior Art In the case of treating a silver halidephotographic material such as a photographic film, a printing paper or adry plate, in general, a hardening bath is often used prior todevelopment processing. The purpose of hardening is to increase thephysical strength of a silver halide photographic emulsion layer and toprevent the emulsion layer from being mechanically and physicallydamaged during processing. The use of a hardening bath is preferable, inparticular, where an emulsion layer has insufficient strength, where theprocessing is carried out for a long period of time or where a hightemperature or high pH treating solution is used. The use of a hardeningbath prior to development is ordinarily referred to as a prehardeningstep." In such a bath an aqueous solution containing at least onehardening agent which hardens gelatin in a photographic emulsion, forexample, aldehydes such as formaldehyde, glyoxal, succinaldehyde andglutaraldehyde is used.

A prehardening bath of this kind hardens an emulsion layer effectivelybut, on the contrary, causes various deleterious effects on photographicproperties, for example, an increase of developing fog, a lowering ofdeveloping density during reversal development and a change of colorforming properties of color formers present in a color light-sensitivematerial.

As a means for removing these disadvantageous photographic influencesdue to the prehardening process,

- it is known to provide a neutralizing bath following the prehardeningprocess. For example, U.S. Pat. No.

3,168,400 discloses the use of an aqueous solution of hydroxylamine orhydrazine as a neutralizing bath. According to this method, the abovementioned disadvantages due to the prehardening step can be overcome,but another disadvantage takes place in that the hydroxylamine orhydrazine is carried over into the subsequent developing step. Sincewater washing is ordinarily not carried out between the neutralizingbath and developing bath in order to simplify the processing, thematerials in the neutralizing bath are carried into the developing bath.As is well known in the art, hydroxylamine or hydrazine, each possessingdeveloping action, causes an unevenness in development as it is carriedout in a developing bath.

It is an object of the present invention to provide a method for thetreatment of a photographic material, whereby good photographicproperties are obtained and sufficient physical strength is provided tothe silver halide emulsion layer. a

It is another object of the invention to provide a neutralizing bathwhich does not adversely influence the photographic properties.

SUMMARY OF THE INVENTION We, the inventors, have found as a result ofvarious In the General paints n R is -CH COOM or CH CH OH and M has thesame meaning as described above.

DETAILED DESCRIPTION OF THE INVENTION The compounds represented by theabove mentioned general formulas (I) and (II) do not possess developingproperties by nature, but have the action of removing a hardener ofaldehyde type carried over from the prehardening bath to theneutralizing bath so as to prevent the hardener from being present inthe subsequent step. While not desiring to be bound by theory, theseremoval properties possibly arise from the characteristics of thesubstituents represented by R and R.

Examples of compounds represented by the above described generalformulas are as follows:

(I) Sulfamic Acid H NSO H (2) Sulfamide H NSO NH (3) Glycine H NCH COOH(4) tris( Hydroxymethyl I-I NC( CH OH aminomethane (5) lminodiaceticacid HN(CH COOH (6) Diethanolamine HN(CH CH OH) Of the above-recitedcompounds, glycine ispreferred.

The neutralizing bath used in the method of the invention comprisesfundamentally an aqueous solution of one or more compounds representedby the foregoing general formulas. These compounds are generally addedto provide a concentration of from about 0.1 to 50 g, preferably 5 to 30g, per 1,000 ml. The neutralizing bath of the invention can optionallycontain a salt, such as sodium sulfate, magnesium sulfate, sodiumacetate and sodium phosphate, to prevent swelling of the gelatin in anamount of about 0 to 200 g/liter, preferably about 50 to I00 g/liter, apH regulator for adjusting the pH such as borax, acetic acid, sodiumacetate, sodium carbonate, sulfuric acid or boric acid, a bufferingagent, such as an organic acid or salt thereof such as acetic acid,citric acid or phthalic acid, acetic acid sodium acetate, tartaric acid,inorganic materials such as boric acid, sodium metaborate, borax, sodiumcarbonate, sodium bicarbonate, potassium metaborate etc., in an amountof about 10 to g/liter, alkali halides such as potassium bromide, sodiumbromide, so-

dium chloride, etc., and other conventional fog inhibitors such asnitrogen containing heterocyclic compounds such as S-nitrobenzimidazole6- nitrobenzimidazole or benzotn'azole 5- nitrobenzotriazole andnitrogen containing heterocyclic mercapto compounds such as l-phenyl-S-mercaptotetrazole, mercaptobenzoxazole, thiouracil, methylbenzothiazole,thioketothiazolidine or 2- mercaptobenzimidazole in an amount of about 1mg to l g/liter and mildew preventing agents, for example, an organicacid an alkali metal salt thereof and an ester thereof such as benzoicacid, sorbic acid, dehydroacetic acid or oxybenzoic acid in an amount ofabout to 2 g/liter. These additives for a neutralizing bath aredisclosed in US. Pat. No. 3,168,400. The neutralizing bath can be usedat any pH range but neutral and acidic pH ranges are desirable to obtainbetter effects. Generally, a pH of about 3 to 7, preferably a pH ofabout 4 to 6 is used;

In the practice of the invention, any prehardener, developer and fixercompositions, which are well known in the art, can be used and theselections thereof can be freely varied in the present invention by anyof skill in the art.

The method of the invention is applicable to the commonly used silverhalide photographic materials comprising a conventional silver halidelight-sensitive material using as a dispersion medium gelatin or anotherhydrophilic high molecular weight material on a support member such asglass, cellulose ester films, polyester films and paper asconventionally used in the art.

The present invention is preferably applied to reversal colorphotographic materials which are processed at a high pH for a long time,for example, as disclosed in US. Pat. Nos. 3,168,400 and 3,582,322, aswell as color papers which are preferably processed at a hightemperature in a rapid manner.

The present invention is carried out after a prehardening bath, forexample, as disclosed in US. Pat. No. 3,168,400 and, after the treatmentbath of the invention, the subsequent processings can be carried out inthe conventional order using known treatment solutions. Generally, thetemperature employed ranges from about 30C to 60C, preferably 32C to50C, with the time being dependent upon the temperature used.

The method of the invention favourably compares with the methods of theprior art because the method of the invention results in lessdevelopment fog, does not cause a lowering of the developing density nora change in the character of color formers in a color photographicmaterial.

The following examples are given to illustrate the invention in greaterdetail without limiting the same. Unless otherwise indicated, all partsand percents are by weight.

EXAMPLE 1 A black-and-white film comprising a panchromaticallysensitized silver iodobromide (AgI: mol%) gelatin emulsion coated onto acellulose acetate film support at 16 mg/ 100cm was exposed using asensitometer and then subjected to the following processings:

The processing solutions used in these processings had the followingcompositions.

Sodium Bisulfite l Formaldehyde (37% aqueous solution) 15 Borax SodiumSulfate Potassium Bromide 2 Water to Glacial Acetic Acid Sodium AcetateAdditive listed below Water to Additive None Sulfamic Acid Glycinetris(Hydroxylmethyl)aminomcthanc lminodiacetic Acid moon DeveloperMonomethyl-p-aminophenol 5 g (5: sulfate) Hydroquinone 2 Sodium SulfiteSodium Hydroxide 1 Sodium Carbonate Monohydrate 41 Potassium Bromide 2Water to 0 Glacial Acetic Acid Water to Fixer Sodium Thiosulfate SodiumSulfite Water to The photographic properties of test films obtained areshown in Table 1.

Relative sensitivity is represented by the logarithmic value of thereciprocal of the exposure quantity corresponding to a blackened densityof fog above 0.l

It can be seen from these properties that the neutralizing bathscontaining the compounds represented by the foregoing general formulasare superior in preventing developing fog effectively as well asincreasing the sensitivity and gamma value. This is true even when waterwashing is practiced between the prehardening and neutralizing. Wheresuch is omitted as is often the case, the effects of this invention areemphasized to an even greater extent.

Since the use of a prehardening bath is made possible by thisneutralizing bath and the physical strengths of the emulsion layer israised, a high temperature processing can be accomplished withoutdifficulty.

EXAMPLE 2 exposed using sensitometer and then subjected to the 7following processings:

Processing Temperature Time Prehardening 37C 2 min 30 sec Neutralizingdo. 30 sec First Developing do. 3 min First Stopping do. 30 sec WaterWashing do. l min Color Developing do. 3 min 30 sec Second Stopping do.30 sec Water Washing do. I min Bleaching do. I min 30 sec Fixing do. 1min Water Washing do. l min The compositions of the processing solutionsused were as follows:.

Prehardener Formaldehyde (37% aqueous solution) Pyruvic Aldehyde (40%)Sulfuric Acid Sodium Sulfate Potassium Bromide Borax 5 Water toNeutralizing Solution Potassium Bromide 2 l 0 Glacial Acetic Acid 0Sodium Hydroxide 6 Sodium Sulfate 50 Additive listed below X Water to 0First Developer Sodium Hexametaphosphate l l-Phenyl-3-pyrazolidone 0Sodium Sulfite 50. Hydroquinone 6. Sodium Carbonate (monohydrate) 35Potassium Bromide 2 Potassium Thiocyanate 1 Potassium Iodide (0.1%aqueous solution) Waterto First Stopping Solution and Second StoppingSolution 25 ml 3 g I000 ml Acetic Acid Sodium Acetate Water to ColorDeveloper I Sodium Hexametaphosphate Benzyl Alcohol Sodium SulfiteTrisodium Phosphate Y 4 Potassium Bromide Potassium Iodide (0.1% aqueoussolution) Sodium Hydroxide e 99 9-9. Ui OMOOQO -Continued First StoppingSolution and Second Stopping Solution 4-Amino-3-methyl-N-ethyl-N- l0.0 g

methanesulfonamidoethylaniline Sulfate Ethylenediamine 8.0 ml

Water to I000 ml Bleaching Solution Potassium Ferricyanide I00 gPotassium Bromide 30.0 g

Water to I000 ml L gfiw L Sodium Thiosulfate I50 g Sodium Sulfite l0 gWater to I000 ml In the above described processings, an additiverepresented by the general formula (I) or (II) was added to theneutralizing solution as shown in the following table. 1

Experiment Additives Quantity F None G Sulfamic Acid 20 g/liter HGlycine 20 g/liter L tris(l-lydroxymethyl)- 20 g/liter aminomethane Theresults obtained are tabulated'below.

Maximum Density Experiment Red Green Blue F 3.52 2.98 3.08 G 3.34 3.123.24 H 3.78 3.09 3.19

As is evident from the results in this table, the maximum density wasincreased by the addition of the compound of theinvention, representedby thegeneral formula (I) or (II), without contamination and otheradverse infiuences upon the photographic properties such as effectivesensitivity.

EXAMPLE 3 Examination of the influence on photographic properties wascarried out when a neutralizing solution was added to the firstdeveloper composition as described in Example 2. 5 percent of each ofthree neutralizing solutions (one containing sulfamic acid as in Example'2 (Experiment G), one containing 20 g/Iiter of hydrazine sulfate asknown in the art (Experiment J) and onecontaining no additive(Experiment F)) was added to the first developer composition. Thephotographic emulsions, exposure conditions and processing steps weresimilar to those employed in Example 2.

The results obtained are tabulated below.

First Maximum Density Neutralizing Solution added to First Developer RedGreen Blue K Neutralizing Solution F 3.41 2.84 3.02 L NeutralizingSolution G 3.48 2.90 3.04 M Neutralizing Solution .l 3.27 2.61 2.72

When the neutralizing solution containing hydrazine was added to thefirst developer, a considerable lowering of the maximum density wasfound, but, on the contrary, substantially no lowering of the maximumdensity in the case of using the neutralizing solution containingsulfamic acid according to the invention was found.

While the invention has been described in detail and with reference tospecific embodiments thereof, it will be apparent to one skilled in theart that various changes and modifications can be made therein withoutdeparting from the spirit and scope thereof.

What is claimed is:

1. In a method for the development of an exposed silver halidephotographic material including a prehardening treatment with analdehyde hardener prior to developing, the improvement which comprisestreating said silver halide photographic material between saidprehardening and said developing with a bath containing a compoundrepresented by the following general formula (I) R-NH 1.

in which R represents M, SO NH CH COOM or -C(CH OH and M represents anatom or group capable of imparting water solubility, or the followinggeneral formula (II) NH (II) R I in which R represents CH COOM or -CH CHOH and M has the same meaning as described above.

2. The method for development of claim I, wherein said compoundrepresented by the general formula (I) or (II) is sulfamic acid,sulfarnide, glycine, tris(hydroxymethyl)aminomethane, iminodiaceticacid, or diethanolamine.

3. The method for development of claim 1, wherein said compoundrepresented by the general formula (I) or (II) is glycine.

4. The method for development of claim 1, wherein said compound of thegeneral fonnula (I) or (II) is present in said bath at a concentrationof from 0.1 to 50 g per 1,000 ml of said bath.

5. The method for development of claim 1, wherein said bath has aneutral or acidic pH.

6. The method for development of claim 1, wherein said bath additionallycontains at least one of a salt, a pH regulator, a buffering agent, analkali halide, a fog inhibitor and a mildew preventing agent.

7. The method for development of claim 1, wherein said bath is at atemperature ranging from about 30C to about 60C.

1. IN A METHOD FOR THE DEVELOPMENT OF AN EXPOSED SILVER HALIDE PHOTOGRAPHIC MATERIAL INCLUDING A PREHARDENING TREATMENT WITH AN ALDEHYDE HARDENER PRIOR TO DEVELOPING, THE IMPROVEMENT WHICH COMPRISES TREATING SAID SILVER HALIDE PHOTOGRAPHIC MATERIAL BETWEEN SAID PREHARDENING AND SAID DEVELOPING WITH A BATH CONTAINING A COMPOUND REPRESENTED BY THE FOLLOWING GENERAL FORMULA (I)
 2. The method for development of claim 1, wherein said compound represented by the general formula (I) or (II) is sulfamic acid, sulfamide, glycine, tris(hydroxymethyl)aminomethane, iminodiacetic acid, or diethanolamine.
 3. The method for development of claim 1, wherein said compound represented by the general formula (I) or (II) is glycine.
 4. The method for development of claim 1, wherein said compound of the general formula (I) or (II) is present in said bath at a concentration of from 0.1 to 50 g per 1,000 ml of said bath.
 5. The method for development of claim 1, wherein said bath has a neutral or acidic pH.
 6. The method for development of claim 1, wherein said bath additionally contains at least one of a salt, a pH regulator, a buffering agent, an alkali halide, a fog inhibitor and a mildew preventing agent.
 7. The method for development of claim 1, wherein said bath is at a temperature ranging from about 30*C to about 60*C. 